Surface-treated titanium dioxide pigments

ABSTRACT

Coated titanium dioxide particles are provided and made from a method wherein a zirconium oxide coating and an aluminum oxide coating are formed on the surface of titanium dioxide particles. The zirconium oxide-forming and aluminum oxide-forming coating materials can be used to control the pH of the surface treatment process without the need for adding pH controlling agents.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No. 11/906,259, filed Oct. 1, 2007, which is incorporated herein in its entirety by reference.

FIELD

The present teachings relate to methods for the preparation of titanium dioxide pigment.

BACKGROUND

Titanium dioxide (TiO₂) is a widely used white pigment popular for its brightness and high refractive index. Titanium dioxide provides whiteness and opacity to products such as paints, coatings, plastics, papers, inks, cosmetics, foods, and medicines.

Titanium dioxide is a photoactive material and TiO₂ particles with size range below 0.2 micron are capable of absorbing ultraviolet light. As a result, electrons can be energized, creating holes in the valence bands and excitons in the conduction bands. In pigment applications, it is important to reduce the photoactivity of titanium dioxide because it can induce undesired redox reactions that degrade paint or coating materials.

In pigment processing, titanium dioxide photoactivity can be reduced by surface treating or coating TiO₂ particles with inorganic and/or electron harvesting materials. These coating materials can prevent ultraviolet light from reaching the surface of the TiO₂ particles. Other materials that can be used are able to quickly harvest or stabilize the energized electrons in the conduction bands before they initiate a redox reaction. For example, oxides of different elements, such as silicon and zinc, as well as different organic chemicals, can be used for this purpose.

The surface treatment of TiO₂ particles with oxide coating is a major processing step in titanium dioxide pigment production. It is a delicate and complex process where reaction conditions such as pH, ionic concentration, and temperature, have to be carefully monitored and adjusted. This is essential to ensure formation of the coating oxide material and to achieve excellent pigment performance. On a manufacturing plant scale, the complexity of the surface treatment process is magnified.

Traditionally, monitoring the pH has been needed not only to ensure that the coating oxide is formed, but also in most cases, to determine the type of the oxide forming. Generally, in surface treatment processes, pH control is carried out using strong acids, such as HCl and HSO₄, and strong alkalis, such as NaOH. Adjusting and controlling the pH, particularly at plant production scale, is a non-trivial step that consumes a large amount of time and chemicals. The use of acids and alkalis also increases the ionic concentration in the aqueous suspension of TiO₂ particles. This can induce unfavorable steric effects in the suspension, causing particles to agglomerate or flocculate, and rendering the surface treatment process ineffective. In addition, a high ionic content can also affect subsequent pigment processing steps. For instance, the efficiency of washing and filtration steps can be affected by the extent of ionic content in the titanium dioxide suspension. The higher the ionic content, the more water is consumed and the more time is needed.

A need exists for a titanium dioxide surface treatment method that utilizes a low ionic content and/or eliminates the use of acids or alkalis to adjust the pH. The method should desirably have a shortened surface treatment process time and provide enhanced efficiency of subsequent washing and filtration steps. The method should also desirably result in effective coating of TiO₂ particles for use as a pigment.

SUMMARY

According to various embodiments, the present teachings provide a method for coating TiO₂ particles with zirconium oxide and aluminum oxide. The method can utilize zirconium oxide-forming and aluminum oxide-forming precursors to adjust and maintain the pH of a titanium dioxide aqueous suspension, without utilizing additional pH controlling materials. The method can be used to prepare titanium dioxide particles for use as a pigment.

According to various embodiments, a method for preparing titanium dioxide pigment can comprise forming an aqueous suspension of TiO₂ particles and then adding a water-soluble zirconium oxide-forming compound to the suspension in an amount such that the pH of the suspension decreases to about 4.0 or lower, to enable formation of a zirconium oxide coating on the TiO₂ particles. A water-soluble aluminum oxide-forming compound can then be added to the suspension in an amount such that the pH of the suspension increases to about 9.0 or higher, and an aluminum oxide coating is formed on the TiO₂ particles. According to various embodiments, the method can be free of adding any additional pH adjustment compounds, other than the water-soluble zirconium oxide-forming compound and the water-soluble aluminum oxide-forming compound.

According to various embodiments, the method for preparing titanium dioxide pigment can further comprise filtering the aqueous suspension to recover the coated TiO₂ particles, washing, and drying the recovered coated titanium dioxide particles. In some embodiments, the recovered TiO₂ particles can be ground and micronized to reach a specific particle size.

According to various embodiments, the present teachings describe a TiO₂ pigment prepared by a method that comprises forming an aqueous suspension of titanium dioxide particles, adding a water-soluble zirconium oxide-forming compound to the suspension in an amount such that the pH of the suspension decreases to about 4.0 or lower, forming a zirconium oxide coating on the TiO₂ particles, adding a water-soluble aluminum oxide-forming compound to the suspension in an amount such that the pH of the suspension increases to about 9.0 or higher, and forming an aluminum oxide coat on the TiO₂ particles. According to various embodiments, the titanium dioxide pigment can be prepared by a method that does not utilize any additional pH adjustment compounds, other than the water-soluble zirconium oxide-forming compound and the water-soluble aluminum oxide-forming compound. In various embodiments, the coated TiO₂ particles can be recovered by filtering the aqueous suspension and washing and drying the recovered coated titanium dioxide particles.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention can be even more fully understood with the reference to the accompanying drawings which are intended to illustrate, not limit, the present invention.

FIG. 1A shows a transmission electron microscopy (TEM) image of TiO₂ particles before surface treatment.

FIG. 1B shows the energy-dispersive x-ray spectroscopy (EDAX) elemental analysis of the TiO₂ particles shown in FIG. 1A.

FIG. 2A shows a TEM image of TiO₂ particles coated with zirconium oxide and aluminum oxide according to an embodiment of the present teachings.

FIG. 2B shows the EDAX elemental analysis of the TiO₂ particles according to various embodiments and shown in FIG. 2A.

DETAILED DESCRIPTION

According to various embodiments of a method for preparing titanium dioxide pigment, TiO₂ particles can be coated with zirconium oxide and aluminum oxide. An aqueous suspension of TiO₂ particles can be prepared having a concentration range of from about 10% to about 50%, or from about 20% to about 40% (weight/volume, i.e, w/v). The overall density of the suspension can be less than about 1.5 g/ml at 25° C. In various embodiments, the TiO₂ particles can initially have an average particle diameter in a range of from about 0.001 microns to about 2.0 microns, or from about 0.01 microns to about 1.0 microns. The average particle size, for example, can be less than 0.5 microns, less than 0.25 microns, or about 0.2 microns.

In various embodiments, the titanium dioxide aqueous suspension can be heated to a temperature in the range of from about 60° C. to about 90° C. The initial pH of the titanium dioxide aqueous suspension can be in a range of from about 5.0 to about 7.0, for example, from about 5.5 to about 6.5, or about 6.0.

According to various embodiments, a water-soluble zirconium compound can then be added to the titanium dioxide aqueous suspension. The water-soluble zirconium oxide-forming compound can comprise, for example, a zirconium sulfate, such as zirconium ortho-sulfate. In some embodiments, the zirconium oxide-forming solution can comprise zirconium chloride, zirconium nitrate, zirconium acetate, zirconium carbonate, zirconium oxychloride, zirconium oxysulfate, and the like. The zirconium oxide-forming solution can have a zirconium ion content of, for example, not less than 10% (w/v). Upon addition of the zirconium oxide-forming solution, according to various embodiments, the pH of the titanium dioxide aqueous suspension can decrease to about 4.0 or lower, for example, to about 3.0 or lower. The decrease in pH can be attributed solely to the addition of the zirconium oxide-forming solution, according to various embodiments, without the addition of any other pH adjusting agents.

In various embodiments, a zirconium oxide coating can then be formed on the TiO₂ particles. The zirconium oxide coating can be allowed to form over a period of time, for example, at least about ten minutes, for example, for about 20 minutes or for about 30 minutes. The suspension can be continually heated and maintained at a temperature in the range of from about 60° C. to about 90° C. In some embodiments, the suspension can be continually stirred while the zirconium oxide coating is formed.

According to various embodiments, a water-soluble aluminum oxide-forming solution can then be added to the resulting zirconium oxide-coated titanium dioxide aqueous suspension. The water-soluble aluminum oxide-forming solution can comprise, for example, sodium aluminate. Other aluminum oxide-forming solutions that can be used can comprise other alkali aluminates, for example, potassium aluminate, tricalcium aluminate, and the like. Upon addition of the aluminum oxide-forming solution, in various embodiments, the pH of the aqueous suspension can increase to at least about 9.0 or greater, for example, to about 9.5 or greater, or to about 10.0. According to various embodiments, the pH increase can be attributed solely to the addition of the aluminum oxide-forming solution, without the addition of any other pH adjusting agents. In various embodiments, an aluminum oxide coating can then be formed on the zirconium oxide-coated TiO₂ particles. The aluminum oxide coating can be allowed to form over a period of time of at least about ten minutes, for example, about 20 minutes, or about 30 minutes. The titanium dioxide suspension can be continually heated and maintained at a temperature of from about 60° C. to about 90° C., or from about 70° C. to about 80° C. In some embodiments, the suspension can be continually stirred while the aluminum oxide coating is formed. In various embodiments, after the aluminum oxide coating is formed, the pH of the resulting suspension can then be brought to within the range of from about 6.0 to about 9.0, for example, in the range of from about 6.5 to about 8.0.

In various embodiments, the coated TiO₂ particles can be separated from the aqueous suspension by filtration. The coated TiO₂ particles can then be washed, for example, with distilled water, so that the final pH of the filtrate is from about 6.0 to about 7.0, or from about 6.0 to about 6.5. The filtered, coated TiO₂ particles can then be dried, ground, and micronised to achieve a specific particle size. The ability to avoid the addition of pH and adjusting agents in the method can result in the conservation of water and time.

The following examples are presented to further illustrate various embodiments of the present teachings.

Example 1

A 40% (w/v) aqueous suspension of TiO₂ particles having a specific gravity of 1.4 g/ml was prepared by dispersing 400 grams of TiO₂ in one liter of distilled water. The pH of the titanium dioxide suspension was adjusted to 6.0±1.0 and the temperature of the suspension was made to be about 60° C. or higher. Then, 13 ml of zirconium ortho-sulfate solution (density 1.12 g/ml) at a concentration not less than 10% (w/v) was added to the titanium dioxide aqueous suspension. The suspension was then left to heat for at least about ten minutes. After that, 37 ml of sodium aluminate solution (density 1.49 g/ml) at a concentration not less than 15% (w/v) was added directly to the titanium dioxide aqueous suspension, resulting in an increase of the pH to greater than 10.0. The final pH was then adjusted to less than 9.0, and the suspension was filtered, washed, dried, ground, and micronised to produce the pigment.

Example 2

The method of preparation was similar to that described in Example 1, except that only 7.5 mls of zirconium ortho-sulfate was added.

Example 3

The method of preparation was similar to that described in Example 1, except that the final pH of the suspension, after adding the sodium aluminate solution, was not adjusted and remained at about 10.0.

Example 4

In this example, the TiO₂ particles were coated with aluminum oxide only. Approximately 45 ml of sodium aluminate were directly added to an aqueous suspension of TiO₂ particles, at a pH of 6.0±1.0. Upon addition of the sodium aluminate, the pH of the aqueous suspension increased to above 10. The titanium dioxide suspension was then heated for 10 minutes at 90° C. before bringing the pH down to 6±2. The titanium dioxide suspension was then further heated for 10 minutes before filtration, drying, grinding, and micronisation of the coated particles.

Comparative Sample

For comparison with Examples 1 to 4, coated TiO₂ particles were prepared according to the method described by Green et al. (U.S. Pat. No. 5,203,916), herein incorporated in its entirety by reference.

Results

FIG. 1A shows a TEM image of TiO₂ particles before surface treatment, according to various embodiments. No oxide coat can be observed on the surface of the particles. This is further confirmed by the EDAX elemental analysis, shown in FIG. 1B. The EDAX analysis shows that no zirconium peak can be detected.

FIG. 2A shows a TEM image of TiO₂ particles after formation of the zirconium oxide and aluminum oxide coating, as prepared in Example 1. TiO₂ particles coated with zirconium oxide and aluminum oxide can be seen on the surface of the particles. This is confirmed by the EDAX elemental analysis shown in FIG. 2B, in which zirconium and aluminum peaks are present.

Table 1 shows the chemical composition of samples prepared according to Examples 1-4, and the Comparison Sample.

TABLE 1 Chemical Composition (by weight %) of coated TiO₂ Samples described in Examples 1-4 ZrO₂ A1₂O₃ TiO₂ Example 1 (%) (%) (%) 1 0.48 3.70 95.82 2 0.23 3.60 96.17 3 0.50 3.80 95.70 4 0.00 3.60 96.40 Comparison Sample 0.46 3.56 95.98

Table 1 confirms the presence of coating oxides (ZrO₂ and Al₂O₃) in the prepared titanium dioxide pigment materials according to embodiments of the present teachings. The Comparison Sample, prepared according to the methods described by Green et al., used additional amounts of pH controlling materials (i.e., additional sulphuric acid and sodium hydroxide). As seen in Table 1, the chemical composition of Example 1 and Example 3 compare favorably to the Comparison Sample. Example 2, prepared similarly to Example 1 but with half the volume of zirconium ortho-sulfate, produced TiO₂ particles coated with about half the amount of zirconium oxide. Example 4, prepared without adding any zirconium compound, produced TiO₂ particles having no zirconium oxide coating. The aluminum oxide coating was unaffected.

As detailed in Table 1, Example 1 and Example 3 compare favorably to the Comparison Sample. The preparation of samples in Examples 1-4, however, was faster than the preparation of the Comparison Sample by at least 15%. This was at least partially due to the elimination of additional steps related to adjusting the pH of the titanium dioxide suspension with additional acids or alkalis, and with easier washing of the samples. For example, the preparation of Examples 1-4 used, at a minimum, at least about 18% less water for the filtrate washing. Furthermore, Examples 1-4 used at least about 25% less acid, and about 100% less alkali, compared to the preparation of the Comparison Sample.

The titanium dioxide pigments produced in Examples 1-4 were further examined to ensure their stability as pigments. For this, two tests were carried out. The first test evaluated the dispersion of samples in alkyd paint resin, as described by Roberts et al. (U.S. Pat. No. 6,544,328 B2), which is incorporated herein in its entirety by reference. The results of the dispersion tests are shown in Table 2.

TABLE 2 Dispersion of TiO₂ samples produced in Examples 1 to 4, in alkyd paint resin. Time After Fineness of Grind At Different Sample Time Intervals (μm) Addition Example Example Example Example (min.) 1 2 3 4 5 30 45 20 20 10 15 20 10 10 15 10 15 10 10 20 10 10 10 10

A second test measured the extent of durability of the samples as pigment, as described by Baidins et al. (U.S. Pat. No. 5,554,216), which is incorporated herein in its entirety by reference. The results of the durability rating are shown in Table 3.

TABLE 3 Durability rating of TiO₂ samples produced in Examples 1 to 4. Durability rating from: Example 1 - 10* 1 8.70 2 7.90 3 10.0 4 3.50 *1 is lowest and 10 is highest durability achieved.

While the present teachings have been described in terms of exemplary embodiments, it is to be understood that changes and modifications can be made that fall within the scope of the present teachings.

The present invention can include any combination of these various features or embodiments above and/or below as set-forth in sentences and/or paragraphs. Any combination of disclosed features herein is considered part of the present invention and no limitation is intended with respect to combinable features.

The entire contents of all references cited in this disclosure are incorporated herein in their entireties, by reference. Further, when an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether such ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining a range.

Other embodiments of the present invention will be apparent to those skilled in the art from consideration of the present specification and practice of the present invention disclosed herein. It is intended that the present specification and examples be considered as exemplary only with a true scope and spirit of the invention being indicated by the following claims and equivalents thereof. 

What is claimed is:
 1. A coated titanium dioxide pigment prepared by a method comprising: (a) forming an aqueous suspension of titanium dioxide particles; (b) adding a zirconium oxide-forming solution to the suspension in an amount sufficient to decrease the pH of the suspension to about 4.0 or lower; (c) forming a zirconium oxide coating on the titanium dioxide particles to form a suspension of coated particles; (d) adding an aluminum oxide-forming solution to the suspension of coated particles in an amount sufficient to increase the pH of the suspension to about 9.0 or higher; and (e) forming an aluminum oxide coating on the coated particles to form a coated titanium dioxide pigment.
 2. The coated titanium dioxide pigment of claim 1, wherein the method further comprises, after step (e): (f) filtering the aqueous suspension to recover the product; and (g) washing and drying the recovered product, such that the coated titanium dioxide pigment is dry.
 3. The coated titanium dioxide pigment of claim 2, wherein the final pH of the washed product is about 6.0.
 4. The coated titanium dioxide pigment of claim 1, wherein pigment comprises a titanium dioxide particle at its core and the titanium dioxide particle has an average particle diameter in a range of from about 0.01 micron to about 1.0 micron.
 5. The coated titanium dioxide pigment of claim 4, wherein the titanium dioxide particle has an average particle diameter of less than or equal to about 0.2 micron.
 6. The coated titanium dioxide pigment of claim 1, wherein the method comprises forming the zirconium oxide coating on the titanium dioxide particles in step (c) over a time period of at least about 10 minutes.
 7. The coated titanium dioxide pigment of claim 1, wherein the method comprises forming the aluminum oxide coating on the coated titanium dioxide particles in step (e) over a time period of at least about 10 minutes.
 8. The coated titanium dioxide pigment of claim 1, having a chemical composition of from 95.70% by weight to 96.40% by weight TiO₂ and from 3.60% by weight to 3.80% by weight Al₂O₃.
 9. The coated titanium dioxide pigment of claim 1, having a chemical composition of from 95.70% by weight to 95.82% by weight TiO₂, from 3.70% by weight to 3.80% by weight Al₂O₃, and from 0.48% by weight to 0.50% by weight ZrO₂.
 10. The coated titanium dioxide pigment of claim 1, having a Baidins et al. durability rating of from 7.90 to 10.0.
 11. A coated titanium dioxide pigment prepared by a method consisting essentially of: (a) forming an aqueous suspension of titanium dioxide particles; (b) adding a zirconium oxide-forming solution to the suspension in an amount sufficient to decrease the pH of the suspension to about 4.0 or lower; (c) forming a zirconium oxide coating on the titanium dioxide particles to form a suspension of coated particles; (d) adding an aluminum oxide-forming solution to the suspension of coated particles in an amount sufficient to increase the pH of the suspension to about 9.0 or higher; and (e) forming an aluminum oxide coating on the coated particles to form a coated titanium dioxide pigment.
 12. The coated titanium dioxide pigment of claim 11, wherein the method consists of steps (a) through (e).
 13. The coated titanium dioxide pigment of claim 11, having a chemical composition of from 95.70% by weight to 96.40% by weight TiO₂ and from 3.60% by weight to 3.80% by weight Al₂O₃.
 14. The coated titanium dioxide pigment of claim 11, having a chemical composition of from 95.70% by weight to 95.82% by weight TiO₂, from 3.70% by weight to 3.80% by weight Al₂O₃, and from 0.48% by weight to 0.50% by weight ZrO₂.
 15. The coated titanium dioxide pigment of claim 11, having a Baidins et al. durability rating of from 7.90 to 10.0.
 16. A coated titanium dioxide pigment prepared by a method comprising: (a) forming an aqueous suspension of titanium dioxide particles; (b) adding an aluminum oxide-forming solution to the suspension of coated particles in an amount sufficient to increase the pH of the suspension to about 9.0 or higher; (c) forming an aluminum oxide coating on the titanium dioxide particles; and (d) filtering and drying the resulting coated titanium dioxide particles, to form a pigment.
 17. The coated titanium dioxide pigment of claim 16, having a chemical composition of 96.40% by weight TiO₂ and 3.60% by weight Al₂O₃. 